CN101356154A - Process for preparing liquid, storage-stable organic isocyanates containing carbodiimide and/or uretonimine groups - Google Patents
Process for preparing liquid, storage-stable organic isocyanates containing carbodiimide and/or uretonimine groups Download PDFInfo
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- CN101356154A CN101356154A CNA2006800505438A CN200680050543A CN101356154A CN 101356154 A CN101356154 A CN 101356154A CN A2006800505438 A CNA2006800505438 A CN A2006800505438A CN 200680050543 A CN200680050543 A CN 200680050543A CN 101356154 A CN101356154 A CN 101356154A
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- Prior art keywords
- ortho ester
- carbodiimide
- ester
- isocyanate
- acid
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- 150000001718 carbodiimides Chemical class 0.000 title claims abstract description 50
- 239000012948 isocyanate Substances 0.000 title claims abstract description 45
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 150000002905 orthoesters Chemical class 0.000 claims description 55
- 150000002148 esters Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- FGWYWKIOMUZSQF-UHFFFAOYSA-N 1,1,1-triethoxypropane Chemical compound CCOC(CC)(OCC)OCC FGWYWKIOMUZSQF-UHFFFAOYSA-N 0.000 claims description 2
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- CWLNAJYDRSIKJS-UHFFFAOYSA-N triethoxymethoxyethane Chemical compound CCOC(OCC)(OCC)OCC CWLNAJYDRSIKJS-UHFFFAOYSA-N 0.000 claims description 2
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 2
- 239000011496 polyurethane foam Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 5
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- -1 according to US-A-2 Chemical class 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical class C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- ZBVOEVQTNYNNMY-UHFFFAOYSA-N O=P1=CCCC1 Chemical class O=P1=CCCC1 ZBVOEVQTNYNNMY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-M carbonochloridate Chemical compound [O-]C(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-M 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VJQGGZWPOMJLTP-UHFFFAOYSA-N octadecane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCC(O)O VJQGGZWPOMJLTP-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/095—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to carbodiimide or uretone-imine groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing liquid, storage-stable, low-color-number, Carbodiimide (CD) -and/or Uretonimine (UI) -group-containing isocyanate mixtures, to the isocyanate mixtures obtainable by this method, and to their use for producing mixtures with other isocyanates and for producing prepolymers containing isocyanate groups and polyurethane plastics, preferably polyurethane foams.
Description
The present invention relates to that a kind of liquid state, stable storing, chromatic number are low, (UI) preparation method of the isocyanate mixture of group of carbodiimide (CD) and/or uretonimine (uretonimine), the isocyanate mixture that makes of method thus, and they contain the prepolymer of isocyanate group and the application in the urethane plastic (optimization polyurethane foam materials) producing with the mixture of other isocyanic ester with in production.
The isocyanate mixture that contains CD and/or UI base can be simply by using the effective catalyst of phosphorus heterocycle amylene (phospholine) series, the effective catalyst of phosphorus oxide heterocyclic pentene (phospholine oxide) series particularly, according to US-A-2,853,473, US-A-6,120,699 and EP-A-515 933 in method produce.
On the one hand, the phosphorus heterocycle amylene catalyzer particularly high catalytic activity of phosphorus oxide heterocyclic pentene catalyzer is desired, so that beginning carbodiimide reaction under the temperature condition of gentleness, but on the other hand, also do not know to have any method can guarantee that the katalysis of phosphorus heterocycle amylene or phosphorus oxide heterocyclic pentene effectively stops without restriction up to now.The isocyanic ester of carbodiimideization tends to take place afterreaction, and promptly they can be because disengage CO
2And release gas.This for example will cause, and pressure increases in the storage tank, particularly under comparatively high temps.
Many trials have been done to seeking the effective means that stops the katalysis of phosphorus heterocycle amylene.Various terminators mention that in the patent specification of for example DE-A-2537685, EP-A-515933, EP-A-609698 and US-A-6120699 these terminators comprise for example halogenide of acid, acyl chlorides (acid chloride), chlorocarbonate, silylated acid and main group element.It is effective inadequately to stop phosphorus heterocycle amylene catalyzer with acid, the wherein also for example form of acyl chlorides existence of acid.
According to telling about of EP-A-515933, by the isocyanate mixture that contains CD/UI of phosphorus heterocycle amylene catalytic preparation with at least with the catalyst system therefor equimolar amount, preferably for example trifluoromethanesulfonic acid trimethyl silyl ester (TMST) of 1-2 times of molar weight stops.Yet, find that in fact the isocyanic ester that contains CD/UI for preparing by this mode is only limited to and is applicable to the preparation prepolymer, promptly these contain the reaction product of isocyanic ester and the polyvalent alcohol of CD/UI.Correspondingly the reaction product by the preparation of the isocyanic ester of polyvalent alcohol and CD/UI modification tends to discharge gas, and this can cause, and pressure raises in the transport container, or causes bubbling in the process of handling these products.
This problem can be avoided by using silylated acid to stop phosphorus heterocycle amylene catalyzer with higher molar equivalent than (for example, the ratio with catalyzer is 5: 1 to 10: 1) according to EP-A-515933.But the chromatic number of isocyanic ester of finding the CD/UI modification of gained in fact, subsequently again is on duty mutually.Therefore, like this too with the prepolymer of their production.
If use the acid termination phosphorus heterocycle amylene catalyzer according to the trifluoromethanesulfonic acid type of US-A-6120699, the result also is the same.The chromatic number of the prepolymer that is made by the isocyanic ester of these CD/UI modifications also increases significantly.
In the isocyanate mixture of preparation liquid state, stable storing, carbodiimide (CD) and/or uretonimine (UI) group, can observe the reactive obviously different of used isocyanic ester sometimes, because the required reaction times is also obviously different.For example, can offset the reaction times and prolong unfriendly by improving temperature of reaction and/or catalyst concn (result is the amount that increases terminator).But this will be referred to procedure and/or security risk and/or quality problems (for example, colour increases).
Therefore, the purpose of this invention is to provide a kind of simple and economic method for preparing liquid state, stable storing, light color, contains the isocyanate mixture of carbodiimide and/or uretonimine groups, this method does not have those above-mentioned defectives, and produces liquid state, stable storing, isocyanate mixture that chromatic number is low.
The present invention relates to the method that a kind of preparation contains the organic isocyanate of carbodiimide and/or uretonimine groups, wherein with phosphorus heterocycle amylene class catalyzer to one or more Kazakhstan gloomy (Hazen) chromatic number≤100APHA, preferably≤organic isocyanate of 50APHA carries out the part carbodiimideization, stop the carbodiimide reaction then, the feature of this method is that carbodiimideization is reflected at ortho ester and carries out under existing.According to this method, the required reaction times can shorten or keep shorter, and/or the amount of required catalyzer can reduce.
According in the method for the present invention, can use the mixture of a kind of ortho ester or several different ortho ester.In the present invention, ortho ester can join in the isocyanate material, perhaps joins in the reaction mixture in the carbodiimide process.Ortho ester is that undiluted form adds with material preferably, perhaps adds as masterbatch (for example as ortho ester at isocyanate material or the solution in the isocyanic ester of carbodiimideization).
In the present invention, breathing out gloomy chromatic number can be according to DIN/EN/ISO 6271-2 (draft, in September, 2002), uses with respect to being that 5 centimetres material is measured with water as object of reference, bed thickness.Employed metering facility can be for example Dr.Lange LICO 300 photometers.
Certainly, the organic isocyanate of higher chromatic number also can be used as raw material.But when using these higher chromatic number isocyanic ester, the advantage of good colour aspect is not fully exploited.
The invention still further relates to the organic isocyanate that contains carbodiimide and/or uretonimine groups that can obtain by aforesaid method.These organic isocyanates that contain carbodiimide and/or uretonimine groups at room temperature are liquid, and depend on CD/UI content and/or employed isocyanic ester, and (for example, 0 ℃) also is liquid at low temperatures.
The present invention also provides according to the application of the organic isocyanate that contains carbodiimide and/or uretonimine groups of the present invention in the mixture of preparation and other isocyanic ester, and the application in the improved prepolymer that contains isocyanate group of preparation chromatic number.
At last, the present invention also provides according to the organic isocyanate that contains carbodiimide and/or uretonimine groups of the present invention and the isocyanate mixture and/or the application of the improved prepolymer of chromatic number in urethane plastic is produced of being produced by their.
Hazen chromatic number≤100APHA, preferred≤any required organic isocyanate of 50APHA all can be used as the raw material of the inventive method.But, preferably be used for carrying out the carbodiimideization of organic diisocyanate according to method of the present invention, and then be used for polyurethane chemistry.
Certainly, the organic isocyanate of higher chromatic number also can be used as raw material.But in the case, the advantage of good colour aspect can not be fully exploited.
Suitable isocyanic ester is for example aromatics, araliphatic, aliphatic series and/or alicyclic diisocyanate and/or polyisocyanates.
The aliphatic series that can mention by the mode that exemplifies and/or the representative of alicyclic diisocyanate are isophorone diisocyanates, 1, hexamethylene-diisocyanate and dicyclohexyl methane diisocyanate (in each situation, can use pure isomer and/or any required isomer mixture).
The representative of the araliphatic vulcabond that can mention by the mode that exemplifies is the various isomer of xylylene diisocyanate (xylidene-diisocyanate).
Aromatic diisocyanate and polyisocyanates, for example the vulcabond of tolylene diisocyanate and diphenylmethane series and polyisocyanates are particularly useful for the present invention.
Particularly, following isocyanic ester is a proper raw material:
Aromatic diisocyanate, such as 2,4-and/or 2,6-tolylene diisocyanate (TDI), 2,2 '-, 2,4 '-and/or 4, any desired mixt of 4 '-diphenylmethanediisocyanate (MDI) and this class aromatic diisocyanate and
The vulcabond of diphenylmethane series and the mixture of polyisocyanates, wherein the content of monomer diphenylmethanediisocyanate isomer is 80 weight % to 100 weight %, the content that is higher than the polyisocyanates of two functional diphenylmethane series is 0 to 20 weight %, wherein the diphenylmethanediisocyanate isomer is by 4 of 0 to 100 weight %, 4 '-diphenylmethanediisocyanate, 2 of 100 weight % to 0 weight %, 2 of 4 '-diphenylmethanediisocyanate and 0 to 8 weight %, 2 '-diphenylmethanediisocyanate is formed, and the percentage ratio sum of three kinds of isomer equals 100 weight %.
The organic isocyanate that is preferably used as raw material is aromatic diisocyanate especially, such as 2, and 4-and/or 2,6-tolylene diisocyanate (TDI), 2,2 '-, 2,4 '-and/or 4, any desired mixt of 4 '-diphenylmethanediisocyanate (MDI) and this class aromatic diisocyanate.Preferred raw material is 2,2 '-, 2,4 '-and/or 4, any desired mixt of 4 '-diphenylmethanediisocyanate (MDI) and this class aromatic diisocyanate, wherein in the raw material (organic isocyanate) 2,2 '-, 2,4 '-and/or 4, the total amount of 4 '-diphenylmethanediisocyanate is at least 85 weight %, the diphenylmethanediisocyanate isomer is by 4 of 0 to 100 weight %, 4 '-diphenylmethanediisocyanate, 2 of 100 to 0 weight %, 2 of 4 '-diphenylmethanediisocyanate and 0 to 8 weight %, 2 '-diphenylmethanediisocyanate is formed, and the summation of given percentage ratio is 100 weight %.Most preferred raw material is 2,2 '-, 2,4 '-and/or 4, any desired mixt of 4 '-diphenylmethanediisocyanate (MDI) and this class aromatic diisocyanate, wherein in the raw material (being organic isocyanate) 2,2 '-, 2,4 '-and/or 4, the total amount of 4 '-diphenylmethanediisocyanate is at least 90 weight %, the diphenylmethanediisocyanate isomer is by 4 of 0 to 100 weight %, 4 '-diphenylmethanediisocyanate, 2 of 100 weight % to 0 weight %, 2 of 4 '-diphenylmethanediisocyanate and 0 to 8 weight %, 2 '-diphenylmethanediisocyanate is formed, and the percentage ratio summation of three kinds of isomer is 100 weight %.The most particularly preferred raw material is 2,2 '-, 2,4 '-and/or 4, any desired mixt of 4 '-diphenylmethanediisocyanate (MDI) and this class aromatic diisocyanate, wherein in the raw material (being organic isocyanate) 2,2 '-, 2,4 '-and/or 4, the total amount of 4 '-diphenylmethanediisocyanate is at least 99 weight %, the diphenylmethanediisocyanate isomer is by 4 of 0 to 100 weight %, 4 '-diphenylmethanediisocyanate, 2 of 100 to 0 weight %, 2 of 4 '-diphenylmethanediisocyanate and 0 to 8 weight %, 2 '-diphenylmethanediisocyanate is formed, and the percentage ratio summation of three kinds of given isomer is 100 weight %.
Carry out in the presence of phosphorus heterocycle amylene class catalyzer according to method of the present invention.Phosphorus heterocycle amylene class catalyzer is known, for example describes to some extent in EP-A-515933 and US-A-6120699.The typical example of these catalyzer is mixtures of phosphorus oxide heterocyclic pentene for example well known in the prior art, as to meet following general formula:
With
Catalyst consumption depends on the quality and/or the reactivity of isocyanate material.Therefore, can be by the simplest concrete amount of easily determining required catalyzer of test in advance.
By using ortho ester, the reactivity of isocyanate material is improved.This is because for example they can offset the reactive effect of minimizing of the accessory constituent that may discharge HCl in the isocyanate material.But, also may have other mechanism of action.
Suitable ortho ester is the ortho ester of carboxylic acid for example.The ortho ester of suitable carboxylic acid has following general structure R
1-(C (OR
2) (OR
3) (OR
4))
n, wherein:
R
1Represent aliphatic, alicyclic, aromatics or araliphatic base, can contain heteroatoms and/or other functional group,
R
2To R
4Represent aliphatic, alicyclic, aromatics or araliphatic base, can contain heteroatoms and/or other functional group,
n≥1。
R
2To R
4Can all identical or whole differences, perhaps R
2To R
4In two bases be identical.Equally, R
2To R
4In two or three bases can be a monomolecular part, thereby have ring or dicyclo ortho ester structure.
The ortho ester of suitable carboxylic acid for example is: the ortho ester of formic acid, for example trimethyl orthoformate, triethyl orthoformate; The ortho ester of acetate, for example trimethyl orthoacetate, triethly orthoacetate; The ortho ester of propionic acid, for example former propionic acid trimethyl, triethyl orthopropionate; Or their mixture.
Mentioned compound only is exemplary; The ortho ester of suitable carboxylic acid is not limited to described compound.
Suitable ortho ester can also be the ortho ester of carbonic acid for example.The ortho ester of suitable carbonic acid has following general structure C (OR
2) (OR
3) (OR
4) (OR
5), wherein:
R
2To R
5Represent aliphatic, alicyclic, aromatics or araliphatic base, can contain heteroatoms and/or other functional group,
R
2To R
5Can all identical or whole differences, perhaps R
2To R
5In two bases be identical, perhaps R
2To R
5In two or three bases be identical.Equally, R
2To R
5In two or two or three bases can be a monomolecular part, thereby have ring or dicyclo ortho ester structure.
The ortho ester of suitable carbonic acid is for example original methyl carbonate and tetraethyl orthocarbonate or their mixture.Mentioned compound only is exemplary; The ortho ester of suitable carbonic acid is not limited to described compound.
Suitable ortho ester also can be the ortho ester of silicic acid for example.The ortho ester of suitable silicic acid has following general structure Si (OR
2) (OR
3) (OR
4) (OR
5), wherein:
R
2To R
5Represent aliphatic, alicyclic, aromatics or araliphatic base, can contain heteroatoms and/or other functional group,
R
2To R
5Can all identical or whole differences, perhaps R
2To R
5In two bases be identical, perhaps R
2To R
5In two or three bases be identical.Equally, R
2To R
5In two or two or three bases can be a monomolecular part, thereby have ring or dicyclo ortho ester structure.
The ortho ester of suitable silicic acid is for example original quanmethyl silicate and tetraethyl orthosilicate or their mixture.Mentioned compound only is exemplary; The ortho ester of suitable silicic acid is not limited to described compound.
Can be before adding catalyzer, add in the catalyzer or only after adding catalyzer, add a kind of ortho ester or the mixture of several different ortho ester.Preferably, ortho ester only adds after adding catalyzer, promptly adds in the process of carbodiimideization.Can determine to add the optimum time point of ortho ester according to simple experiment in advance, preferably reach required isocyanic ester total conversion rate 50%, more preferably 30%, preferred especially 20% before add.
Equally, can determine the optimum amount of ortho ester according to simple experiment in advance, be benchmark in the weight of used isocyanic ester, preferred≤1, and 000ppm, more preferably≤250ppm, preferred≤100ppm especially.
Thereby ortho ester can join in the isocyanate material, perhaps adds in the reaction mixture in the process of carbodiimideization.In the present invention, ortho ester is that undiluted form adds with material preferably, perhaps adds as masterbatch (for example as ortho ester at isocyanate material or the solution in the isocyanic ester of carbodiimideization).
Use ortho ester can obtain the reactivity of higher carbodiimide reaction, thereby shorten the amount of reacting the required time and/or reducing required catalyzer.
The carbodiimide reaction is carried out under 50 ℃ to 150 ℃ temperature routinely, preferably carries out under 60 ℃ to 100 ℃.But, very high temperature of reaction also be fine (that is, up to about 280 ℃).The optimal reaction temperature of carbodiimide reaction depends on the character of used isocyanate material and/or catalyzer, and available test is simply in advance determined.
The carbodiimide reaction generally reaches 3% to 50% in carbodiimide degree (" carbodiimide degree " is the percentage ratio of the total amount of the isocyanate groups that exists in respect to isocyanate material of the isocyanate groups of carbodiimideization), preferably reach at 5% to 30% o'clock is interrupted.
The carbodiimide degree can be determined by measuring NCO% in the process of carrying out in the inventive method, and NCO% for example determines by volumetry well known by persons skilled in the art or suitable on-line analysis method.Suitable on-line analysis method is for example near-infrared analysis or middle infrared analysis.
The carbodiimide degree also can be determined by the amount of the carbonic acid gas of for example overflowing from reaction mixture in the process that the inventive method is carried out.Like this, the cubing value of this carbonic acid gas just in time provides the information of the carbodiimide degree that relevant any moment reached.
In addition, other suitable off-line known to those skilled in the art or online course monitoring method also can use in principle.
In order to stop the carbodiimide reaction, preferably uses in catalyzer as benchmark at least equimolar amount, more preferably the excessive 1-20 of mole number doubly, the most preferably excessive 1-10 of mole number times preferred trifluoromethanesulfonic acid trimethyl silyl ester (TMST) or the mixture of alkylating agent or above-mentioned terminator.In this case, alkylating agent or trifluoromethanesulfonic acid trimethyl silyl ester (TMST) preferably use as unique terminator.
The ester or trialkyl oxygen (trialkyloxonium) compound of the ester that preferred alkylating agent is a trifluoromethanesulfonic acid, mineral acid (preferred inorganic acid).
The reaction product of carbodiimide reaction can contain colour stabilizer, such as those colour stabilizers that are routinely added in the isocyanic ester.In this case, the moment of adding stablizer is not vital.Colour stabilizer can join in the isocyanic ester as raw material before the carbodiimide reaction, perhaps joins in the reaction product after the carbodiimide reaction finishes.Equally, can not only in raw material but also in reaction product, add colour stabilizer.This class stablizer is normally known to those skilled in the art, comprises, for example, is selected from the material of sterically hindered phenol, phosphorous acid ester or sterically hindered amines.In each situation, colour stabilizer can use separately, perhaps with identical or different material type in the mixture of other typical material use.The consumption of colour stabilizer changes on the order of magnitude well known by persons skilled in the art, usually being benchmark as the isocyanic ester of raw material or the reaction product of carbodiimide reaction, for independent stablizer or mixture, its consumption is 100ppm to 10000ppm.
The prepolymer that contains isocyanate group is made by organic isocyanate that contains carbodiimide and/or uretonimine groups that makes according to method of the present invention and the conventional polyol reaction in the polyurethane chemistry.Suitable polyvalent alcohol is that molecular weight is that 62 gram/moles are to 599 gram/moles, be preferably the simple polyvalent alcohol of 62 gram/moles to 300 gram/moles, such as ethylene glycol, TriMethylolPropane(TMP), 1, the 2-propylene glycol, 1,2-butyleneglycol or 2, the 3-butyleneglycol, hexylene glycol, ethohexadiol, dodecanediol and/or octadecandiol, particularly original known molecular weight is that 600 gram/moles are to 8000 gram/moles in the polyurethane chemistry, be preferably high molecular weight polyether and/or the polyester polyol of 800 gram/moles to 4000 gram/moles, this family macromolecule quantizes compound and contains at least two usually, normally 2 to 8, preferred 2 to 4 primary hydroxyls and/or secondary hydroxyls.The example of this type of polyvalent alcohol for example is disclosed in, and US 4218543, the 7 hurdles the 29th walk in the 9th hurdle the 32nd row.
According to the advantage of method of the present invention is conspicuous: owing to have ortho ester in the carbodiimide process, the reactivity of reaction mixture increases and/or by stdn.As a result, required reaction times shortens or keeps shorter, and/or the amount of required catalyzer reduces.Contain the isocyanic ester of carbodiimide and/or uretonimine groups and all also have good preservation stability and more shallow color by the prepolymer that this isocyanic ester prepares.
These contain the organic isocyanate of carbodiimide and/or uretonimine groups and the prepolymer by the preparation of isocyanic ester of the present invention and polyol reaction is the quite valuable raw material that is used to prepare urethane plastic, and wherein the preparation of urethane plastic realizes through isocyanic ester polyaddition reaction method by isocyanic ester of the present invention or its prepolymer and polyvalent alcohol (for example polyether glycol and/or polyester polyol).
Embodiment:
Raw material:
-Desmodur
, Bayer Materialscience AG (Bayer AG) (4,4 '-ditan-vulcabond, NCO content: 33.6 weight %)
The catalyzer of-phosphorus oxide heterocyclic pentene class: the industrial grade mixture of 1-methyl isophthalic acid-oxo-1-phosphorus heterocycle penta-2-alkene and 1-methyl isophthalic acid-oxo-1-phosphorus heterocycle penta-3-alkene, the concentration in toluene is 1 weight %
-terminator: trifluoromethanesulfonic acid trimethyl silyl ester (TMST)
Use following general remark to prepare the organic isocyanate that contains carbodiimide and/or uretonimine groups:
10 kilograms are breathed out gloomy chromatic number＜15APHA, contain 750ppm 3, the technical grade 4,4 of 5-di-t-butyl-4-hydroxytoluene '-MDI (Desmodur
, Bayer Materialscience AG (BayerMaterialScience AG)) and at N
2/ be heated to about 90 ℃ under stirring.The catalyst solution that adds the amount described in the table then is to realize required catalytic amount.The ortho ester of adding respective amount in reaction mixture (moment of adding, the thing quality and quantity of adding sees the following form; A: triethly orthoacetate).With reaction mixture at N
2/ be heated to about 95 ℃ under stirring, up to reaching required NCO content.Add terminator trifluoromethanesulfonic acid trimethyl silyl ester (TMST) then and stop the carbodiimide reaction, then mixture was stirred 1 hour.
The result is summarised in the following table.
Breathing out gloomy chromatic number uses with respect to being that 5 centimetres material is measured with water as object of reference, bed thickness according to DIN/EN/ISO 6271-2 (draft, in September, 2002).The metering facility that uses is Dr.Lange LICO300 photometer.
Comparative Examples 1 and Comparative Examples 2 have illustrated that the quantity of hydrolyzable chlorine increases the disadvantageous effect to reactivity or reaction times.In the foundation embodiments of the invention,, compare reactivity with Comparative Examples 2 and be improved for the hydrolyzable chlorine of same amount; After 360 minutes, the nco value of Comparative Examples 2 only drops to 31.6% from initial about 33.6%, and embodiments of the invention drop to 29.5%.
The comparative descriptions of Comparative Examples 1 and embodiments of the invention by adding ortho ester, when the content of hydrolyzable chlorine is double, still can obtain suitable reactivity, promptly can realize identical nco value with the suitable reaction times.
Claims (18)
1. method for preparing the organic isocyanate of carbodiimide and/or uretonimine groups, wherein with phosphorus heterocycle amylene class catalyzer to one or more breathe out gloomy chromatic number≤100APHA, preferably≤organic isocyanate of 50APHA carries out the part carbodiimideization, stop the carbodiimide reaction then, it is characterized in that carbodiimideization is reflected under the ortho ester existence carries out.
2. the method for claim 1 is characterized in that, uses the ortho ester of carboxylic acid.
3. the method for claim 1 is characterized in that, the ortho ester of described carboxylic acid has general structure R
1-(C (OR
2) (OR
3) (OR
4))
n, wherein: R
1Represent aliphatic, alicyclic, aromatics or araliphatic base, it can randomly contain heteroatoms, and can randomly have other functional group; R
2To R
4Represent aliphatic, alicyclic, aromatics or araliphatic base, it can randomly contain heteroatoms, and can randomly have other functional group, n 〉=1.
4. the method for claim 1 is characterized in that, uses the ortho ester of formic acid, acetate or propionic acid.
5. the method for claim 1 is characterized in that, uses trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethly orthoacetate, former propionic acid trimethyl, triethyl orthopropionate or their mixture as ortho ester.
6. the method for claim 1 is characterized in that, uses the ortho ester of carbonic acid.
7. the method for claim 1 is characterized in that, the ortho ester of described carbonic acid has general structure C (OR
2) (OR
3) (OR
4) (OR
5), R wherein
2To R
5Represent aliphatic, alicyclic, aromatics or araliphatic base, it can contain heteroatoms and/or other functional group.
8. the method for claim 1 is characterized in that, uses original methyl carbonate, tetraethyl orthocarbonate or their mixture as ortho ester.
9. the method for claim 1 is characterized in that, uses the ortho ester of silicic acid.
10. the method for claim 1 is characterized in that, the ortho ester of described silicic acid has general structure Si (OR
2) (OR
3) (OR
4) (OR
5), R wherein
2To R
5Represent aliphatic, alicyclic, aromatics or araliphatic base, it can contain heteroatoms and/or other functional group.
11. the method for claim 1 is characterized in that, uses original quanmethyl silicate, tetraethyl orthosilicate or their mixture as ortho ester.
12. as each described method in the claim 1 to 11, it is characterized in that, before adding catalyzer, when adding catalyzer or after the adding catalyzer, add described ortho ester.
13., it is characterized in that as each described method in the claim 1 to 12, be benchmark in the weight of used isocyanic ester, the concentration of described ortho ester≤1,000ppm, preferred≤250ppm, more preferably≤100ppm.
14. method as claimed in claim 12 is characterized in that, described ortho ester adds with the form of material.
15. method as claimed in claim 12 is characterized in that, described ortho ester as isocyanate material or the masterbatch in the isocyanic ester of carbodiimideization add.
16. by the carbodiimide that makes as each described method in the claim 1 to 15 and/or the organic isocyanate of uretonimine groups.
17. the application of the organic isocyanate of carbodiimide as claimed in claim 16 and/or uretonimine groups in the preparation isocyanate mixture.
18. the application of the organic isocyanate of carbodiimide as claimed in claim 16 and/or uretonimine groups in preparation prepolymer or urethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006000825A DE102006000825A1 (en) | 2006-01-05 | 2006-01-05 | Process for the preparation of liquid, storage-stable carbodiimide-containing organic isocyanates |
| DE102006000825.1 | 2006-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101356154A true CN101356154A (en) | 2009-01-28 |
Family
ID=37989832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800505438A Pending CN101356154A (en) | 2006-01-05 | 2006-12-27 | Process for preparing liquid, storage-stable organic isocyanates containing carbodiimide and/or uretonimine groups |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US7662989B2 (en) |
| EP (1) | EP1973870A1 (en) |
| JP (1) | JP2009522418A (en) |
| KR (1) | KR20080090500A (en) |
| CN (1) | CN101356154A (en) |
| DE (1) | DE102006000825A1 (en) |
| WO (1) | WO2007076999A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107250190A (en) * | 2015-02-26 | 2017-10-13 | 科思创德国股份有限公司 | The method for preparing the composition comprising poly- carbodiimide with improved storage stability |
| CN108586706A (en) * | 2018-04-18 | 2018-09-28 | 万华化学集团股份有限公司 | The method for preparing the modified isocyanate mixture containing carbodiimides and/or uretonimine analog derivative |
| CN111689874A (en) * | 2020-07-11 | 2020-09-22 | 万华化学（宁波）有限公司 | Method for reducing color number of carbodiimide modified organic isocyanate, low-color-number isocyanate and application thereof |
| CN111747867A (en) * | 2020-06-28 | 2020-10-09 | 万华化学（宁波）有限公司 | Preparation method of low-color-number low-VOC (volatile organic compounds) modified isocyanate |
| CN116283666A (en) * | 2023-02-15 | 2023-06-23 | 万华生态科技有限公司 | Preparation method of high-purity 4,4' -diphenylmethane diisocyanate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006000822A1 (en) * | 2006-01-05 | 2007-07-12 | Bayer Materialscience Ag | Process for the preparation of liquid, storage stable carbodiimide and / or uretonimine containing organic isocyanates |
| DE102006000833A1 (en) * | 2006-01-05 | 2007-07-12 | Bayer Materialscience Ag | Process for the preparation of liquid, storage stable carbodiimide and / or uretonimine containing organic isocyanates |
| AR073417A1 (en) * | 2008-10-29 | 2010-11-03 | Basf Se | SUPPORT AGENT |
| US9714378B2 (en) * | 2008-10-29 | 2017-07-25 | Basf Se | Proppant |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2853473A (en) | 1956-08-27 | 1958-09-23 | Du Pont | Production of carbodiimides |
| GB1356851A (en) * | 1971-06-11 | 1974-06-19 | Ici Ltd | Isocyanate/uretonimine compositions for polyurethanes |
| DE2504334A1 (en) * | 1975-02-01 | 1976-08-05 | Bayer Ag | HIGH MOLECULAR, INSOLUBLE CARBODIIMIDIZATION CATALYSTS |
| DE2537685C2 (en) | 1975-08-23 | 1989-04-06 | Bayer Ag, 5090 Leverkusen | Process for the partial carbodiimidization of the isocyanate groups of organic polyisocyanates |
| DE2606419A1 (en) * | 1976-02-18 | 1977-08-25 | Basf Ag | STORAGE-STABLE, LIQUID POLYISOCYANATE CONTAINING CARBODIIMIDE GROUPS AND METHOD FOR THEIR MANUFACTURING |
| US4284730A (en) * | 1980-02-07 | 1981-08-18 | Basf Wyandotte Corporation | Liquid carbodiimide- and uretonimine-isocyanurate-containing polyisocyanate compositions and microcellular foams made therefrom |
| DE4117384A1 (en) | 1991-05-28 | 1992-12-03 | Bayer Ag | METHOD FOR THE PRODUCTION OF LIQUID, STORAGE-STABLE CARBODIIMIDE AND / OR URETONIMIN GROUPS HAVING ORGANIC ISOCYANATES, AND THE USE THEREOF FOR THE PRODUCTION OF POLYURETHANE PLASTICS |
| DE4302697A1 (en) | 1993-02-01 | 1994-08-04 | Bayer Ag | Process for the production of organic carbodiimides and their use as plastic stabilizers |
| JPH0867662A (en) * | 1994-08-30 | 1996-03-12 | Sumitomo Bayer Urethane Kk | Production of liquid diphenylmethane diisocyanate |
| US6120699A (en) | 1998-09-21 | 2000-09-19 | Basf Corporation | Storage stable methylene bis(phenylisocyanate) compositions |
| DE102004033849A1 (en) * | 2004-07-13 | 2006-02-16 | Bayer Materialscience Ag | Process for the preparation of liquid, storage-stable carbodiimide and / or uretonimine containing organic isocyanates having a low color number |
| DE102004060038A1 (en) | 2004-12-14 | 2006-06-22 | Bayer Materialscience Ag | Process for the preparation of liquid, storage-stable carbodiimide and / or uretonimine containing organic isocyanates having a low color number |
| DE102006000822A1 (en) | 2006-01-05 | 2007-07-12 | Bayer Materialscience Ag | Process for the preparation of liquid, storage stable carbodiimide and / or uretonimine containing organic isocyanates |
| DE102006000833A1 (en) | 2006-01-05 | 2007-07-12 | Bayer Materialscience Ag | Process for the preparation of liquid, storage stable carbodiimide and / or uretonimine containing organic isocyanates |
| DE102006002158A1 (en) | 2006-01-17 | 2007-07-19 | Bayer Materialscience Ag | Process for the preparation of liquid, storage-stable carbodiimide and / or uretonimine containing organic isocyanates |
-
2006
- 2006-01-05 DE DE102006000825A patent/DE102006000825A1/en not_active Withdrawn
- 2006-12-27 WO PCT/EP2006/012552 patent/WO2007076999A1/en active Application Filing
- 2006-12-27 CN CNA2006800505438A patent/CN101356154A/en active Pending
- 2006-12-27 EP EP06841178A patent/EP1973870A1/en not_active Withdrawn
- 2006-12-27 JP JP2008548948A patent/JP2009522418A/en not_active Withdrawn
- 2006-12-27 KR KR1020087019154A patent/KR20080090500A/en not_active Application Discontinuation
-
2007
- 2007-01-03 US US11/649,000 patent/US7662989B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107250190A (en) * | 2015-02-26 | 2017-10-13 | 科思创德国股份有限公司 | The method for preparing the composition comprising poly- carbodiimide with improved storage stability |
| CN107250190B (en) * | 2015-02-26 | 2021-03-26 | 科思创德国股份有限公司 | Method for producing compositions comprising polycarbodiimides with improved storage stability |
| CN108586706A (en) * | 2018-04-18 | 2018-09-28 | 万华化学集团股份有限公司 | The method for preparing the modified isocyanate mixture containing carbodiimides and/or uretonimine analog derivative |
| CN108586706B (en) * | 2018-04-18 | 2021-06-29 | 万华化学集团股份有限公司 | Process for preparing modified isocyanate mixtures containing carbodiimide and/or uretonimine derivatives |
| CN111747867A (en) * | 2020-06-28 | 2020-10-09 | 万华化学（宁波）有限公司 | Preparation method of low-color-number low-VOC (volatile organic compounds) modified isocyanate |
| CN111747867B (en) * | 2020-06-28 | 2022-08-02 | 万华化学（宁波）有限公司 | Preparation method of low-color-number low-VOC (volatile organic compounds) modified isocyanate |
| CN111689874A (en) * | 2020-07-11 | 2020-09-22 | 万华化学（宁波）有限公司 | Method for reducing color number of carbodiimide modified organic isocyanate, low-color-number isocyanate and application thereof |
| CN116283666A (en) * | 2023-02-15 | 2023-06-23 | 万华生态科技有限公司 | Preparation method of high-purity 4,4' -diphenylmethane diisocyanate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009522418A (en) | 2009-06-11 |
| DE102006000825A1 (en) | 2007-07-12 |
| WO2007076999A1 (en) | 2007-07-12 |
| US7662989B2 (en) | 2010-02-16 |
| US20070155938A1 (en) | 2007-07-05 |
| KR20080090500A (en) | 2008-10-08 |
| EP1973870A1 (en) | 2008-10-01 |
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